CN104927841B - A kind of near-infrared organic fluorescent dye with mechanical response - Google Patents
A kind of near-infrared organic fluorescent dye with mechanical response Download PDFInfo
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- CN104927841B CN104927841B CN201510336333.6A CN201510336333A CN104927841B CN 104927841 B CN104927841 B CN 104927841B CN 201510336333 A CN201510336333 A CN 201510336333A CN 104927841 B CN104927841 B CN 104927841B
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Abstract
A kind of near-infrared organic fluorescent dye with mechanical response, it it is the kermesinus crystalline, powder with following general structural formula compound, described crystalline, powder be by by described compound dissolution in the organic solvent that can be dissolved, rotary evaporation in vacuo obtains after removing organic solvent.Organic fluorescent dye of the present invention is transformed into amorphous state by crystalline state after mechanical force, the lower naked eyes red color visible fluorescence that can send 620nm is excited at blue light, absolute fluorescence quantum yield more than 11%, after organic vapor is stifling, crystalline state can be converted to again by amorphous state, fluorescence inactivates, and fluorescence quantum yield is 0.Above characteristic has good application prospect at the aspect such as false proof, stress spy/detection, sensor, fluorescent probe.
Description
Technical field
The present invention relates to a kind of organic fluorescent dye, the organic fluorescent dye of the present invention can send red after mechanical force
Color fluorescence.
Background technology
Organic fluorescent dye obtains in organic electroluminescent LED, organic solid laser instrument, the field such as bioluminescence imaging
To being widely applied so that it is become the study hotspot of science and industrial quarters.Particularly red fluorescence dyestuff, owing to it is three bases
Important component part in color RGB colour developing scheme entirely, and red light outclass other face to the penetrance of bio-tissue
Color, can be used for biological fluorescent labelling and imaging etc., develop organic red fluorescent dye have important Research Significance and application before
Scape.
Most of organic fluorescent dyes are to have strong fluorescent emission in weak solution, the most but show unstressed configuration
Or fluorescence is more weak, this significantly limit the actual application of organic fluorescent dye, because generally requiring organic in actual applications
Fluorescent dye exists with state of aggregation or solid state.Particularly there is the organic dyestuff that mechanical response is luminous, at sensor, fluorescence
The fields such as probe have potential using value.
Owing between lowest excited state and the ground state of red fluorescence dyestuff, energy level difference is less, often excited state dye molecule
Nonradiative decay is more effective, and the fluorescence quantum yield causing most of red fluorescence dyestuff is the highest, and the conjunction of this type of dyestuff
Become to need more complicated step.Therefore, the organic dyestuff sending out near-infrared or HONGGUANG at present with mechanical response is relatively fewer.
Summary of the invention
It is an object of the invention to provide a kind of near-infrared organic fluorescent dye with mechanical response.The present invention's is organic
Fluorescent dye is transformed into amorphous state by crystallite state after mechanical force, excites the lower naked eyes that can send 620nm at blue light
Red color visible fluorescence.
The near-infrared organic fluorescent dye with mechanical response of the present invention is to have following general structural formula (I) table
The kermesinus crystalline, powder of the compound shown.
。
In formula, R is C4～C8Alkyl.
Said structure lead to compound that formula (I) represents with 1,3-indenes diketone as drawing electron group, benzene-(3-alkylated substituted thiazoline
Fen)-benzene is conjugated bridge, has drawing electron group-conjugated bridge-drawing electron group molecular characterization.
Preferably, described R is hexyl.
Wherein, described general structure (I) represent the crystalline, powder of compound be by by described compound dissolution can
In the organic solvent dissolved, rotary evaporation in vacuo obtains after removing organic solvent.
The above-mentioned organic fluorescent dye of the present invention at least can use following method to prepare: 3-alkyl replaces-2,5-two
(4-Fonnylphenyl) thiophene and 1,3-indenes diketone, in ethanol solution, carries out Knoevenagel under acetic acid and triethylamine catalysis
Condensation reaction, obtains the solid product of organic fluorescent dye shown in logical formula (I), and being dissolved in by the solid product obtained can be by it
In the organic solvent dissolved, rotary evaporation in vacuo rapidly removes organic solvent, obtains the crystalline, powder of described organic fluorescent dye.
The reaction equation of above-mentioned preparation method is as follows.
。
Wherein, it is possible to the organic solvent that described organic fluorescent dye dissolves is preferably dichloromethane or oxolane.
In above-mentioned Knoevenagel condensation reaction, 3-alkyl-2,5-bis-(4-Fonnylphenyl) thiophene and 1,3-indenes diketone
Consumption mol ratio be 1: 2～2.2.
The structure of the above-mentioned near-infrared organic fluorescent dye with mechanical response by proton nmr spectra (1H-NMR)
Characterize with Matrix Assisted Laser Desorption time-of-flight mass spectrometry (MALDI-TOF-MS) and confirm.
X ray diffracting spectrum shows, dissolves organic fluorescent dye of the present invention in organic solvent through vacuum rotating
After evaporation rapidly removes solvent, the sample powder obtained is crystalline state.After the mechanical force such as grinding, extruding, described organic
Fluorescent dye can be converted to amorphous state by crystalline state.
Fluorescence emission spectrum research display, the crystalline, powder of organic fluorescent dye of the present invention excites lower without meat at blue light
The observable fluorescent emission of eye produces, and fluorescence quantum yield is 0；But after mechanical force is converted to amorphous state, at blue light
Excite down and can send the macroscopic red fluorescence of about 620nm, absolute fluorescence quantum yield more than 11%.
What is more important, of the present invention is converted to amorphous organic fluorescent dye steam fumigating through organic solvent
After steaming, can be converted to crystalline state by amorphous state again, fluorescence inactivates, and fluorescence quantum yield is 0.
It is demonstrated experimentally that the presence or absence of organic fluorescent dye red fluorescence of the present invention, mechanical force can be passed through and have
Machine solvent is stifling alternately, produces the inverible transform no less than 5 times.The organic fluorescent dye of this character display present invention
At the aspect such as false proof, stress spy/detection, sensor, fluorescent probe, all there is good using value.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the crystalline state organic fluorescent dye of the embodiment of the present invention 2 preparation.
Fig. 2 is that the embodiment of the present invention 2 organic fluorescent dye is ground is converted into the X ray diffracting spectrum after amorphous state.
Fig. 3 is that the embodiment of the present invention 2 organic fluorescent dye is ground be converted into amorphous state after, the material object under blue light excites
Photo.
Fig. 4 is that the embodiment of the present invention 2 organic fluorescent dye is ground is converted into the fluorescence emission spectrogram after amorphous state.
Fig. 5 is that the embodiment of the present invention 2 organic fluorescence contaminates through mechanical force, then after dichloromethane steam is stifling, in indigo plant
Light excite under photo in kind.
Fig. 6 is the ground fluorescence volume fumigating alternately 5 processes with organic solvent of the embodiment of the present invention 2 organic fluorescent dye
Sub-productivity change collection of illustrative plates.
Detailed description of the invention
Specific examples below is used for further illustrating technical scheme, to be better understood from the present invention
Hold, but these embodiments are not limited to the present invention.
Embodiment 1
Addition 3-butyl-2 in 50mL round-bottomed flask, 5-bis-(4-Fonnylphenyl) thiophene 139.4mg (0.4mmol),
1,3-indenes diketone 128.6mg (0.88mmol), adds dehydrated alcohol 15mL and dissolves, be simultaneously introduced several acetic acid and triethylamine, room
Reaction is stirred under temperature.After question response is complete, stands and be filtrated to get aubergine powder, with dehydrated alcohol recrystallization, obtain cerise
Spicule.Cerise spicule is dissolved completely in dichloromethane, vacuum rotary evaporator rapidly removes solvent dichloro
Methane, obtains the organic fluorescent dye dark red powder 215.7mg of crystalline state, yield 89.2%.
1H-NMR (400 MHz, CDCl3, ppm): δ= 8.57~8.53 (q, 4H); 8.04~8.00 (m, 4H);
7.92 (s, 1H); 7.90 (s, 1H); 7.84~7.81 (m, 4H); 7.76 (d, 2H); 7.65 (d, 2H);
7.41 (s, 1H); 2.75 (t, 2H); 1.68 (m, 2H); 1.36 (m, 2H); 0.85 (t, 3H)。
MALDI-TOF-MS:[M]+ cacld. C40H28O4S, 604.1708; found: 604.1707。
Embodiment 2
Addition 3-hexyl-2 in 50mL round-bottomed flask, 5-bis-(4-Fonnylphenyl) thiophene 150.6mg (0.4mmol),
1,3-indenes diketone 128.6mg (0.88mmol), adds dehydrated alcohol 15mL and dissolves, be simultaneously introduced several acetic acid and triethylamine, room
Reaction is stirred under temperature.After question response is complete, stands and be filtrated to get aubergine powder, with dehydrated alcohol recrystallization, obtain cerise
Spicule.Cerise spicule is dissolved completely in dichloromethane, vacuum rotary evaporator rapidly removes solvent dichloro
Methane, obtains the organic fluorescent dye dark red powder 220mg of crystalline state, yield 86.9%.
1H-NMR (400 MHz, CDCl3, ppm): δ= 8.58~8.54 (q, 4H); 8.05~8.01 (m, 4H);
7.93 (s, 1H); 7.89 (s, 1H); 7.85~7.82 (m, 4H); 7.78 (d, 2H); 7.66 (d, 2H);
7.43 (s, 1H); 2.78 (t, 2H); 1.72 (m, 2H); 1.39 (m, 2H); 1.31 (m, 4H); 0.89
(t, 3H)。
MALDI-TOF-MS:[M]+ cacld. C42H32O4S, 632.2021; found: 632.2019。
The organic fluorescent dye dark red powder preparing the present embodiment carries out X-ray diffraction analysis, its collection of illustrative plates such as Fig. 1,
The appearance of sharp diffraction peak shows that it is crystalline state sample.This crystalline state sample excites lower naked eyes not observe fluorescence at blue light.
After being ground in mortar by above-mentioned dark red powder, again carry out X-ray diffraction sign, its spectrogram such as Fig. 2, bag-like
Curve shows that it has been converted into amorphous state sample.
Fig. 3 show grinding after organic fluorescent dye photo in kind under 400nm blue light excites, it can be seen that its
Going out macroscopic red fluorescence, test its fluorescence emission spectrum such as Fig. 4, maximum emission wavelength is 620nm, fluorescence quantum yield
11.7%。
After fumigating the amorphous state sample after grinding with dichloromethane steam, as it is shown in figure 5, excite lower naked eyes not see at blue light
Observe visible fluorescence.
Above-mentioned sample is ground-and organic steam is stifling alternately, can realize checker with presence or absence of red fluorescence.Fig. 6
Show the fluorescence quantum yield situation of change that sample is carried out 5 inverible transforms.
Claims (4)
1. there is an organic fluorescent dye for mechanical response, be there is compound that following general structural formula (I) represents dark
Red crystalline powder,
In formula, R is C4～C8Alkyl；
Wherein, described general structure (I) represents that the crystalline, powder of compound is at dichloromethane or four by described compound dissolution
In hydrogen furan, rotary evaporation in vacuo obtains after removing solvent.
Organic fluorescent dye the most according to claim 1, is characterized in that described R is hexyl.
3. the preparation method of the organic fluorescent dye with mechanical response described in claim 1, is in ethanol solution, 3-
Alkyl-2,5-two (4-Fonnylphenyl) thiophene carries out Knoevenagel with 1,3-indenes diketone under acetic acid and triethylamine are catalyzed
Condensation reaction, is dissolved in dichloromethane or oxolane by the solid product obtained, and rotary evaporation in vacuo obtains institute after removing solvent
State the organic fluorescent dye of crystalline, powder shape；Alkyl therein is C4～C8Alkyl.
The preparation method of the organic fluorescent dye with mechanical response the most according to claim 3, is characterized in that described
3-alkyl-2,5-two (4-Fonnylphenyl) thiophene is 1: 2～2.2 with the consumption mol ratio of 1,3-indenes diketone.
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